Colorant and additive concentrate carrier system with efficacy over a wide range of polymeric processing temperatures

ABSTRACT

A concentrate carrier system for adding colorants and/or other additives to resin formulations over a broad range of processing temperatures is described. The carrier system includes at least 20 wt. % of a base acrylate copolymer, such as ethyl-methyl acrylate, provided in combination with less than 55 or less than 30 wt. % of a ring-opened cyclic ester or ether derivative, such as polycaprolactone, polyhydroxyalkonates, polyglycolide, polylactide, poly(butylene succinate), other aliphatic linear polyesters. The remainder, which may include an optional organic plasticizer such as epoxidized soybean oil, is dedicated to an additive package that may include colorants, property enhancers, and/or non-property fillers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 16/354,986 filed on Mar. 15, 2019 and now granted as U.S. Pat.No. 11,053,361, which is incorporated by reference.

TECHNICAL FIELD

The present invention relates to non-liquid compositions and methods forintroducing colorants and other additives to a variety of thermoplasticand/or thermosetting resins having a wide range of processingtemperatures, from engineered polymers to common, lower-meltingpolymers.

BACKGROUND

Thermoplastic and thermosetting resin systems are used in a wide rangeof manufactured articles. Depending upon intended use, these systemsneed to meet certain structural and/or aesthetic requirements.Consequently, a variety of colorant and additive packages andconcentrates exist to enable manufacturers to customize resin systems totheir specific needs.

One challenge is that these colorant and additive packages must becompatible with the processing temperature inherent to the base resin.In this regard, industrial or “engineered” resin systems often requireprocessing temperatures in excess of 200° C. Examples of such engineeredplastics include styrene acrylonitrile (SAN), high-impact polystyrene(PS), acrylonitrile-butadiene-styrene (ABS), polybutylene terephthalate(PBT), polyethylene terephthalate (PET), polyoxymethylene (POM),polycarbonate (PC), thermoplastic polyether (TPE), thermoplasticpolyurethane (TPU), various polyamides, and other known systems. Theindividual melt temperatures of each of these resins is known in the artand specifically disclosed herein. The comparatively high processingtemperatures for these systems require concentrates that do not degradeor otherwise experience phase separation and plating at thesetemperatures.

In contrast, lower melting point polymeric compositions may be preferredbased upon cost, equipment, ease of use, availability, and/or otherrequirements. These materials can typically be processed at temperaturesbetween 95° to 175° C., and they encompass a wide range of compositionsincluding (but not limited to) polyethylene (PE), such as peroxide- ormoisture-crosslinkable polyethylene (XLPE) and other highly-substitutedpolyolefins, and lactones, such as polycarpolactone. Notably, these lowtemperature systems may include thermoplastic and thermosettingmaterials and, as above, their melt temperatures are specificallycontemplated and disclosed herein.

In order to be an effective colorant or additive concentrate, thecarrier resin for that concentrate must liquefy below the lowest end ofthe desired subset of base polymers (i.e., engineered resins and lowermelting point resins) but otherwise remain viable (i.e., does notdegrade) throughout the desired temperature range. Consequently, anumber of “universal” carrier systems for pigments and other additiveshave been proposed that are provided in liquid form.

While these liquids can be effective carrier systems for colorants andadditives in both high and low temperature resins, the use of liquids ischallenging to formulators. Foremost, it is often difficult tointroduce, evenly disperse, and retain the liquid among component blendsthat are primarily solid resin pellets. Examples of such a liquidcarrier can be found in U.S. Pat. Nos. 4,167,503 and 5,308,395, as wellas Chinese Publication CN102504599A.

Other solutions have been proposed. U.S. Pat. No. 3,846,360 describes apigment carrier vehicle for resins melting in the range of 250° to 400°C., while a styrene-butadiene-styrene (SBS) block copolymer carrier isproposed for temperature above 230° C. in U.S. Pat. No. 6,713,545.

United States Patent Publication 2009/0162683 discloses a biodegradablepolyester resin with 0.1 to 5 wt. % of metal alkyl sulfonate as animpact modifier. This allows the resultant material to remainsubstantially free of any glycerin fatty acid esters. However, thisdisclosure is limited to the use of polyesters as a base resin, and noconsideration is given to colorants or additive packages.

Conversely, U.S. Pat. No. 4,810,733 discloses a color concentrate basedupon polypropylene and polypropylene or polyethylene wax. Still othercarriers and concentrate systems can be found in United States PatentPublications 2002/0198122 and 2004/0214927, as well as U.S. Pat. No.7,935,747. Japanese Publications JPH5202234 and JPH11106573, as well asPatent Cooperation Treaty Publications WO2007/138120 and WO2011/014528are also noteworthy.

As additional background, resin systems, equipment, andassociated/relevant technologies which could be incorporated with a“universal” concentrate (i.e., a solid concentrate/carrier that can beused in both high and low temperature resins/formulations) are describedin U.S. Pat. Nos. 2,916,481; 3,837,773; 3,786,018; and 5,589,545.Additionally, United States Patent Publications 2008/0317990 and2016/0017144; Patent Cooperation Treat Publications WO2002/018487,WO2009/002653, and WO2014/050580; Japanese Publication JP2000248074; andChinese Publication CN101831099 are all noteworthy. As seen in thesepublications, the coating of wires and cables is of particular interestinsofar as regulations and standards place very specific conditions onthe thickness, composition, and physical characteristics of thesepolymeric coatings.

SUMMARY

A carrier platform for colorants and/or other additives is described.The carrier includes a base acrylate copolymer used in combination witha ring-opened cyclic ester or ether derivative. In some embodiments, anoptional organic plasticizer is provided in combination with an additivepackage that may include colorants, property enhancers, and non-propertyfillers. The resulting concentrate serves as a solid, universalconcentrate, appropriate for adding to both low and high melting resinsystems.

In a first embodiment, a solid concentrate carrier system for use inthermoplastic or thermosetting resin formulations is contemplated. Theconcentrate carrier system includes any combination of the following:

-   -   an acrylate copolymer comprising at least 20 wt. % of the        concentrate;    -   a ring-opened cyclic ester or ether derivative, preferably        formed as a linear aliphatic polyester element, comprising at        least one of: polycaprolactone, polyhydroxyalkanoates or        polyhydroxyalkonates (PHAs), polyglycolide, polylactide,        poly(butylene succinate), and any of the foregoing optionally        having one or more functional groups pendant thereto, said        polycaprolactone element comprising less than 30 wt. % of the        concentrate;    -   a plasticizer comprising between 0.5 and 30 wt. % of the        concentrate;    -   an additive package comprising a remainder of the concentrate,        said additive package including at least one selected from:        colorants, property enhancers, and non-property fillers;    -   wherein the concentrate retains a solid form at ambient        temperatures and the additive package remains viable in low        melting resin systems and engineered resin systems at processing        temperatures ranging from 90° C. or less up to at least 200° C.;    -   wherein the acrylate polymer includes ethyl-methyl acrylate        copolymer;    -   wherein the acrylate copolymer is less than 50 wt. % of the        concentrate;    -   wherein the plasticizer consists essentially of epoxidized        soybean oil;    -   wherein the additive package is at least 50 wt. % of the        concentrate;    -   wherein the additive package is at least 75 wt. % of the        concentrate;    -   wherein only polycaprolactone is provided and said        polycaprolactone is 5 wt. % or less of the total concentrate;    -   wherein only polycaprolactone is provided;    -   wherein the a ring-opened cyclic ester or ether derivative is        selected from: polyhydroxyalkonates, polyglycolide, polylactide,        and copolymers of lactone and one or more additional monomers;    -   wherein a ring-opened cyclic ester or ether derivative includes        any of: (i) polymers of functionalized caprolactone, polymer of        caprolactone, (ii) polymers functionalized lactone having a ring        structure containing between 2 to 6 carbons within the ring        structure, (iii) polymers of lactone having a ring structure        containing between 2 to 6 carbons within the ring        structure, (iv) copolymers of functionalized lactone having a        ring structure containing between 2 to 6 carbons within the ring        structure and at least one branched and/or straight chain        aliphatic monomer having between 2 and 20 carbons in total, said        monomers further containing optional carboxyl and/or hydroxyl        functional groups, and (v) copolymers of lactone having a ring        structure containing between 2 to 6 carbons within the ring        structure and at least one branched and/or straight chain        aliphatic monomer having between 1 and 20 carbons in total, said        monomers further containing optional carboxyl and/or hydroxyl        functional groups;    -   wherein, when present, the functionalized caprolactone and/or        the functionalized lactone include at least one functional group        selected from: carboxyl, hydroxyl, methyl, butyl, propyl, and        isopropyl;    -   wherein the at least one monomer is one or more selected from        methyl, butyl, propyl, and isopropyl structures;    -   wherein the additive package includes at least one selected        from: organic and inorganic pigments, dyes, alumina, mica,        perlescent effects, laser markers, and metallocene polyethylene;    -   wherein the additive package includes at least one selected        from: zinc stearate, calcium-fatty acid, process modifiers, a        mold release agent, a biocide, a UV stabilizer, a heat        stabilizer, an anti-oxidant, a radical scavenger, an acid        scavenger, an anti-static filler, and a conductive filler; and    -   wherein the additive package includes at least one selected        from: calcium carbonate, clay, silica, talcum powder, rice husk        ash, and ash.

In another embodiment, a solid concentrate carrier system for use inresin formulations having processing temperatures ranging from 90° C. orless up to at least 200° C. consists essentially of any combination ofthe following:

-   -   17.0 to 45.0 wt. % of ethyl-methyl acrylate copolymer;    -   3.0 to 5.0 wt. % of at least one selected from:        polycaprolactone, polyhydroxyalkonates, polyglycolide,        polylactide, and any of the foregoing optionally having one or        more functional groups pendant thereto;    -   0.0 to 20.0 wt. % of plasticizer;    -   an additive package consisting of 2.0 to 30.0 wt. % (relative to        the concentrate carrier system) of colorants, 0.8 to 18.5 wt. %        (relative to the concentrate carrier system) of property        enhancers, and 0.0 to 41.0 wt. % (relative to the concentrate        carrier system) of non-property fillers;    -   wherein the plasticizer is provided between 0.5 to 20.0 wt. %;    -   wherein the plasticizer consists essentially of epoxidized        soybean oil;    -   wherein the property enhancers consist of at least one selected        from: a process modifier, a UV stabilizer, and an anti-oxidant;    -   wherein the process modifier is zinc stearate and/or        calcium-fatty acid;    -   wherein the non-property filler is provided between 27.2 and        41.0 wt. %;    -   wherein the non-property filler consists essentially of calcium        carbonate;    -   wherein the additive package only includes colorants and        property enhancers; and    -   wherein the property enhancers are provided at or less than 1.3        wt. %.

Specific reference is made to the appended claims and description below,all of which disclose elements of the invention. While specificembodiments are identified, it will be understood that elements from onedescribed aspect may be combined with those from a separately identifiedaspect. In the same manner, a person of ordinary skill will have therequisite understanding of common processes, components, and methods,and this description is intended to encompass and disclose such commonaspects even if they are not expressly identified herein.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a differential scanning calorimetry (DSC) plot of the acrylateand ring-opened components of the pre-mix according to one aspect of theinvention.

FIG. 2 is a thermogravimetric analysis (TGA) thermogram of one aspect ofthe invention.

DETAILED DESCRIPTION

Reference may be made in detail to exemplary embodiments of the presentinvention, some of which are illustrated, exemplified, and/or describedherein. Other embodiments and means of carrying out the invention can beutilized, encompassing various structural, compositional, and/orfunctional changes known to those having skill in this field, withoutdeparting from the intended scope. As such, the following description ispresented by way of illustration only and should not limit thesealternatives and modifications in any way.

As used herein, the words “example” and “exemplary” mean an instance orillustration but do not necessarily indicate a key or preferred aspector embodiment. The word “or” is intended to be inclusive rather anexclusive, unless context suggests otherwise. As an example, the phrase“A employs B or C,” includes any inclusive permutation (e.g., A employsB; A employs C; or A employs both B and C). As another matter, thearticles “a” and “an” are generally intended to mean “one or more”unless context suggest otherwise.

As noted above, there is a need for a solid composition that can serveas a platform to create concentrates or masterbatch-type compositionsthat can used be with equal efficacy in low-melting thermoplasticformulations and in combination with engineered resin systems.Manufacturers would welcome a concentrate system that could be used forall their needs. As used herein, the term colorant or additiveconcentrate refers to a solidified resin-based carrier system, formedfrom the pre-mix disclosed below (which may include an optional liquidplasticizer), and subsequently introduced as a solid into any number oflow or high temperature resin formulations.

To that end, a pre-mix of an acrylate copolymer and a ring-openedpolymeric cyclic ester or polymeric ether is created. Generallyspeaking, the acrylate comprises between 20 to 90 wt. % of the pre-mix,while the ring-opened component is provided at less than 30 wt. % of thepre-mix or in other embodiments at between 0.1 to 20 wt. %. Theremainder includes the colorant and additive package, as well as anoptional plasticizer that, when present, may form between 0.5 to 35 wt.% of the pre-mix.

Particular utility has been found in acrylates made from ethylenebutyl-, ethyl-, and methyl-acrylate copolymers. Any combination (orsingle one) of these acrylates may be employed, although ethyl-methylacrylate (EMA) copolymers are preferred in certain aspects. Otheracrylate copolymers may be used, so long as the resulting component(s)provide relatively high temperature stability (in comparison to thepre-mix's other components). Preferably, this acrylate component (or, inaggregate, combination of components) comprises at least 20 wt. %, atleast 30 wt. %, at least 40 wt. %, at least 50 wt. %, at least 60 wt. %,at least 70 wt. %, or at least 80 wt. % of the total pre-mix.Conversely, these components should be no more than 90 wt. %, no morethan 80 wt. %, no more than 70 wt. %, no more than 60 wt. %, no morethan 50 wt. %, no more than 40 wt. %, or no more than 30 wt. % of thetotal pre-mix. Additional limitations and parameters are encompassed bythe examples appended hereto, all of which form part of this writtendisclosure.

Similarly, polycaprolactone and components based from thepolycaprolactone ring structure are preferred as the ring-openedcomponent. Polycaprolactone is particularly useful because of its broadHansen interaction radius, wide availability, and relatively low cost(in comparison to other ring-opened polymeric esters and polymericethers. Certain substituted or functionalized derivatives ofpolycaprolactone and other cyclic ethers are also contemplated. While anominal amount of ring-opened component(s) (i.e., at least 0.1 wt. % ofthe pre-mix) is needed, it should not exceed 30 wt. %. In furtherembodiments, maximum amounts of 1 wt. %, 5 wt. %, 10 wt. %, 15, 20, and25 wt. % of polycaprolactone (or other aliphatic linear polyester orring-opened components) are contemplated, as well as examples identifiedbelow. Notably, any of these stated intervals also can serve as theminimum end of an acceptable range. In some aspects, the aliphaticlinear polyester might serve as a substitute for some or practically allof the acrylate (e.g., polylactide can replace ethyl-methyl acrylate).

While polycarpolactone is expected to have particular utility, it may bepossible to substitute or augment its use with certain polycaprolactonederivatives (i.e., a ring-opened cyclic ester or ether derivatives). Asnoted above, these derivatives may have certain functional groupsintroduced along the carpolactone ring or cyclic ether ring. Three,four, five, and six member ring structures may be preferred for theiravailability and cost. Some examples of derivatives could include:polyhydroxyalkonates, polyglycolide, polylactide, and copolymers oflactone and one or more additional monomers. Poly(butylene succinate) isanother useful substitute/derivative expressly embraced within thisclass for purposes of this application. All of the above can beseparately characterized as aliphatic linear polyester elements.Polyesters having a melting point of 150° to 160° C. or less (andmeeting the other criteria set forth herein) are expected to haveparticular utility as aliphatic linear polyester elements.

Thus, as used herein, “a ring-opened cyclic ester or ether derivative”and/or “aliphatic linear polyester elements” may embrace polymers offunctionalized caprolactone and/or poly(butylene succinate), copolymersand one or more monomers, and/or polymers of those elements. Inparticular, the lactones of interest include ring structures containing2, 3, 4, 5, or 6 carbons, with functional groups possibly appended to one or more of these carbons. In certain embodiments, no functional groupsare added to the lactone ring. When used, monomers for these derivativesare selected from branched and/or straight chain aliphatic structureshaving any whole number of carbon atoms between 1 to 20 within thestructure. These base monomers may include any number of carboxylic orhydroxyl functional groups, as well as methyl, butyl, ethyl, andisopropyl structures (with or without carboxyl and/or hydroxylfunctionalities). The functional groups for monomers can also servepreferred functional groups for polycaprolactone and/or lactone ringstructures.

One advantage of certain aliphatic linear polyester elements relates tobiodegradability. That is, over time, these polymers can degrade intosmaller molecules, such as carbon dioxide, water, nitrogen, etc. underaerobic or anaerobic conditions, usually brought on by action ofenzymes, microorganisms, or catalysts. Polycaprolactone, polylactide,and poly(butylene succinate) are particularly well known in this regard.As government regulations and general concern for polymeric wastecontinue to evolve, biodegradable concentrates and additives areexpected to have particular utility in formulations and variousmanufactured products.

In some aspects, a plasticizer is provided to the pre-mix to wet thepolymer surfaces, thereby lowering the processing temperatures required.For example, epoxidized soybean oil (ESO) can be added in an amountbetween 0.5 to 35 wt. % of the pre-mix, with additional minimum ormaximum levels at 1.0 wt. %, 5 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25wt. %, and 30 wt. % also disclosed. Notably, while ESO and otherplasticizers may be liquid when introduced during the manufacture of thepre-mix for the concentrate carrier system, the final concentratecarrier itself will be solid.

When used, the ESO may be mixed directly into the pre-mix or additivepackage blend. In some embodiments, the pre-mix and additive package arecombined, although a split stream process could be used to separatelymelt the polymers and the additive package prior to forming theconcentrate. Within this context, it will be understood the plasticizerrelates to the processing of the pre-mix, and any desiredcharacteristics to be delivered to the final formulation in which theconcentrate is used would be properly considered as part of the propertyenhancers in the additive package itself. However, formulators may alsoopt to use a plasticizer, including ESO, in the low or high meltingresin formulations enabled by the inventive carrier system.

That said, the additive package forms a significant aspect of theinvention, insofar as the acrylate base and ring-opened component merelyserve as a base resins carrier. Thus, within the confines of creating astable, solid product, it is desirable to optimize and maximize theweight percentage of the additive package relative to the base resinscarrier. In some embodiments, the additive package components compriseat least 0.1 wt. % and, more preferably between 45 wt. % to 55 wt. %,with the remainder of the mass of the pre-mix constituting base resinscarrier (and plasticizer, to the extent a plasticizer is used). In someembodiments, the additive package approaches 80 wt. % of the totalpre-mix. Additionally, the additive package may be 5 wt. %, 10 wt. %, 15wt. %, 20, wt. %, 25 wt. %, 30 wt. %, 35 wt. %, 40 wt. %, 50 wt. %, 65wt. %, 70 wt. %, and 75 wt. % the entire mass of the pre-mix.

The additive package itself may include one, two, or all three of:colorants, property enhancers, and non-property fillers. Each arefamiliar to those of skill in the art, and it will be understood thatthe items used in the additive package must be compatible with oneanother without degrading the final, intended purpose of the concentrate(both as a colorant or additive vehicle, as well as remaining in solidform for its universal use in low and high temperature resinformulations). Colorants are expected to have particular utility incertain aspects of the invention, and this disclosure expresslycontemplates embodiments where colorants are the sole aim of theadditive package or where the pre-mix is optimized for colorants suchthat colorant is the majority component in the additive package withonly small amounts of process modifiers and/or anti-oxidants (less than10 wt. % and, more preferably, less than 5 wt. % of the mass of theadditive package).

Generally speaking, the colorants may be any combination of organic andinorganic pigments, dyes, alumina, mica, perlescent effects, lasermarkers, and/or metallocene polyethylene. To the extent these componentsare referenced or identified in any of the cited publications herein,such portions of those publications are incorporated by reference tofurther inform this disclosure. Additionally, specific examples areidentified below, although these examples should not be taken asnecessarily limiting this disclosure.

Property enhancers impart specific characteristics to the finalthermoplastic formulations (rather than the pre-mix or concentratecarrier system itself). Thus, to the extent a property enhancer isincluded in the additive package of any claimed or disclosed embodiment,those properties are delivered to the formulation into which theconcentrate is introduced. The properties of interest generally includeprocess modifiers and mold release agents, as well as biocides, UV andlight stabilizers, thermal/heat stabilizers, anti-oxidants, radicalscavengers, acid scavengers and anti-static or conductive fillers.Combinations of these property enhancers can be included in any givenconcentrate formulation according to some aspects of the invention. Aswith the colorants, certain non-limiting examples are provided below.

Finally, non-property fillers can be used in the additive package. Thesefillers are not intended to alter the appearance or otherwise impartspecific properties to the concentrate/final resin. Thus, unlike thecolorants and property enhancers, these non-property fillers areintended to facilitate the formulation of the concentrate carrier systemitself. Examples of non-property fillers appropriate to the inventioninclude calcium carbonate, clays, silica, talcum powder, rice husk ash,and certain other, non-reactive types of ash. Reasons for relying onsuch non-property fillers may be related to controlling costs, improvingthe manufacture/processing of the carrier system, and/or ensuring theconcentrate is sufficiently solid.

In one aspect of the invention, the additive package includes a smallamount of metallocene polyethylene for facilitating the processing ofcertain portions of the additive package itself (in this context, themetallocene could be characterized as a non-property filler). Thecomponents of the additive package are pre-compounded in a twin screwextruder before being recombined downstream with the pre-mixpolymer/plasticizer blend. In another embodiment, the additive packageis mixed dry with the pre-mix polymers and plasticizer(s) and thencoagulated in a melt to form the concentrate.

The additive package itself may consistent entirely of colorants. Inother aspects, colorant(s) form the majority of the package, by weightpercentage (i.e., at least 50 wt. %). Property enhancers and/or nonproperty fillers may be added to the colorant(s). In some instances, thenon-property fillers may constitute a majority of the package. Propertyenhancers will typically constitute no greater than 50 wt. % of thepackage. In preferred embodiments, colorants constitute at least 2.5 wt.%, at least 25.0% wt. %, and up to 95.8 wt. % of the additive package.When provided, non-proprety fillers may be anywhere from 50.0 to 60.0wt. % of the package. Property enhancers may be from 2.0 wt. % up to25.0 wt. % of the additive package.

In another aspect, the pre-mix polymers, plasticizer(s), and additivepackage will be combined on a two-roll mill, compounder, single- ortwin-screw extruder, or Farrel continuous mixer. Combinations of thesemixing approaches can also be employed. After mixing, the mixture isthen run through a die or a shower head for pelletizing, or taken as aribbon to be diced.

In this regard, the invention includes methods of making the carriersystem, as well as formulations for that system. Still other aspects ofthe invention relate to the subsequent use of the carrier system incombination with low or high melt processing resins, as noted above.

As described, concentrates (including the additive package) formed inthis manner provide advantages in comparison to existing so-called“universal” or multifunctional concentrates. In particular, theinventive concentrate can be incorporated into low-temperature resins,such as moisture-cure XLPE, while also being suitable for hightemperature engineering resins, especially PC, ABS, and/or Nylon 6.

U.S. Pat. No. 7,442,742 describes a masterbatch composition relying on ametallocene polymer, while U.S. Pat. No. 9,969,881 and a currentlycopending continuing application (filed on Apr. 13, 2018 as U.S. Ser.No. 15/952,926 and now published as United States Patent Publication2018/0258237) describe a split stream process for making suchcompositions. Certain aspects of these disclosures, including theformulations and methods of manufacture, may further inform aspects ofthe invention. As such, these documents are incorporated by reference intheir entirety herein.

Finally, a range of publications describe polymer blends that might beparticularly useful when employed in combination with certain aspects ofthe invention. These documents include: U.S. Pat. Nos. 3,459,834;3,524,906; 4,320,212; 4,404,248; and 4,908,397, as well as Germanpublications DE3518538 and DE 3662527 and Patent Cooperation Treatypublication WO 2008/001684.

In practice, use of the inventive concentrate could enable two shotmanufacturing processes with a combination of differing resin systems(i.e., those whose processing temperatures differ by at least 20° C., atleast 50° C., and up to at least 100° C.) while relying on the sameconcentrate platform. Further, owing to its adaptability over a largerange of processing temperatures, the risk of degradation or loss of theconcentrate (including the desired additive package) is reduced.

One significant aspect of the concentrate carrier system described andclaimed herein is its ability to remain effective and viable across abroad range of temperatures. In turn, this means the concentrate can beincorporated into low or high temperature processes without fear of theconcentrate degrading or failing to perform as intended. The viabilityof the concentrate can be verified by way of oxidation induction timeand/or melt-separation tests, as well as known standards forthermogravimetric analysis, such as ASTM E1131, E2105, and the like. Ingeneral, the concentrate needs to retain its integrity and avoid carbonformation or separation during use. Final formulations exhibiting lumps,speckling, and/or other similar traits are indicative of a concentratecarrier system that has failed to melt within the formulation asintended/needed.

In other aspects, the ratios of components within the additive package,as well as the relative ratio of base resins (i.e., acrylate andpolycaprolactone) to the entire additive package, are significant. Thus,all of the disclosed weight percentages herein may be further combinedto form ratios in certain embodiments. In determining such ratios, theamount of plasticizer introduced to the pre-mix may be disregarded. Inthat same manner, the relative ratios of plasticizer, base resins, andadditive package are contemplated and within these disclosed aspects.

EXAMPLES

Table 1 shows three exemplary formulations for the pre-mix and additivepackage according to certain aspects of the invention. All componentsidentified with the exception of plasticizer are selected to be insolid, rather than liquid or gaseous, forms.

TABLE 1 Concentrate formulations. All values expressed as wt. % of thetotal pre-mix. Component Sample 1 Sample 2 Sample 3 Acrylate Poly-EMA,20% MA 45 43.83 17 Ring-opened Polycaprolactone, linear MW ~50 k 5.04.87 3.0 Plasticizer Epoxidized soybean oil (ESO) 0.7 20 0.5 Additivepackage 48.3 31.3 79.5 (total) (total) (total) Colorants in/organicpigment 12.42 ^(1a) 30 ^(2a ) 2.0 ^(3a) dyes — — — alumina — — — mica —— — pearlescent effects — — — laser markers — — — Property enhancersProcess modifier 0.8 ^(1b) 0.3 0.5 Mold release agent — — — Biocide — —— UV stabilizer — — 15.0 Heat stabilizer — — — Anti-oxidant — 1.0 ^(2b)3.0 ^(3b) Radical scavengers — — — Acid scavengers — — — Anti-static orconductive filler — — — Metallocene PE — — — Flame retardants — — —Non-property fillers Calcium carbonate 27.2 — 41 Clay — — — Silica — — —Talcum powder — — — Rice husk and other ash — — — ^(1a) combination ofC.I. pigments red (48:2) at 1.0%, blue (15:1) at 8.76%, black (7 at 70nm) at 0.66%, and white (6) at 2.0% ^(1b) 0.4% zince stearate and 0.4%calcium-fatty acid ^(2a) C.I. pigment black (7) ^(3a) C.I. pigment white(6) ^(2b) and ^(3b) Irganox 1010

Sample 1 was mixed by hand and then melt compounded on a two-roll mill,with temperature set to 205° F. for the front roll and 130° F. for theback roll. Sample 1 was shown to provide uniform color at all testedquantities (up to 5 phr) in the following polymer resins: rigid andflexible polyvinyl chloride, XLPE, poly(vinylidene fluoride),high-density polyethylene, polypropylene, polyoxymethylene, ABS, generalpurpose- and high-impact PS, PC, Nylon 6, and TPE.

As a control experiment, a comparable concentrate based upon theteachings of U.S. Pat. No. 6,713,545 was created using a linear diblockcopolymer of styrene and ethylene/propylene. This material remainedrubbery at lower temperatures and was extremely difficult to compoundbelow 280° F. It could not be compounded with XLPE, and plated whenattempting to compound it with PVC.

Differential scanning calrimetry (DSC) of poly(ethylene-co-methylacrylate), trade name Elvaloy AC1820, and polycaprolactone are shown inFIG. 1 , showing that the melt temperature for this material is 92° C.(198° F.). The embodiment of the invention described above was tested ina melt flow indexer to demonstrate that it could be dispersed at thistemperature using ASTM D1248, with the temperature set to 93° C. Themelt flow index of this embodiment of the invention was found to be 0.01g/10 min (2.16 kg, 93° C.). At 190° C., the melt flow of this materialwas found to be 2.38 g/10 min (2.16 kg).

FIG. 2 shows a dry air TGA thermogram of the above-representedembodiment of the invention. The temperatures of 1% mass loss at 305.6°C. (582° F.) and a minor degradation onset at 325.7° C. (618.3° F.).This is sufficient to allow the concentrate to be compounded with hightemperature polymers that require the material to reach 600° F. forshort periods, such as PC.

Sample 2 was produced using a Farrel continuous mixer and extrudersystem to produce pelletized industry-scale quantities. Sample 3 wasproduced using a two-roll mill as described above. Both Samples 1 and 3maintained sufficient integrity and could be sectioned into uniformpieces from the solid mill sheet. Sample 2 could be pelletized using anunderwater-cut pelletizing die.

Although specific embodiments have been illustrated, described, and/orexemplified in this specification, it is to be understood that theinvention is not to be limited to just the embodiments disclosed, andnumerous rearrangements, modifications and substitutions are alsocontemplated. The exemplary embodiment has been described with referenceto the preferred embodiments, but further modifications and alterationsencompass the preceding detailed description. These modifications andalterations also fall within the scope of the appended claims or theequivalents thereof.

What is claimed is:
 1. A concentrate and carrier system for use inthermoplastic or thermosetting resin formulations, the concentratecomprising: an acrylate copolymer comprising at least 20 wt. % of theconcentrate; a ring-opened cyclic ester or ether derivative comprisingat least one of: polyhydroxyalkonates, polyglycolide, polylactide,poly(butylene succinate), and any of the foregoing optionally having oneor more functional groups pendant thereto, said ring-opened cyclic esteror ether derivative comprising less than 30 wt. % of the concentrate; anadditive package comprising a remainder of the concentrate, saidadditive package including at least one selected from: colorants,property enhancers, and non-property fillers; and wherein theconcentrate retains a solid form at ambient temperatures and theadditive package remains viable in low melting resin systems andengineered resin systems at processing temperatures ranging from 90° C.or less up to at least 200° C.
 2. The concentrate of claim 1 wherein theacrylate polymer includes ethyl-methyl acrylate copolymer.
 3. Theconcentrate of claim 1 wherein the acrylate copolymer is less than 50wt. % of the concentrate.
 4. The concentrate of claim 1 wherein theadditive package is at least 50 wt. % of the concentrate.
 5. Theconcentrate of claim 1 wherein the additive package is at least 75 wt. %of the concentrate.
 6. The concentrate of claim 1 wherein the additivepackage includes at least one selected from: organic and inorganicpigments, dyes, alumina, mica, perlescent effects, laser markers, andmetallocene polyethylene.
 7. The concentrate of claim 1 wherein theadditive package includes at least one selected from: zinc stearate,calcium-fatty acid, process modifiers, a mold release agent, a biocide,a UV stabilizer, a heat stabilizer, an anti-oxidant, a radicalscavenger, an acid scavenger, an anti-static filler, and a conductivefiller.
 8. The concentrate of claim 1 wherein the additive packageincludes at least one selected from: calcium carbonate, clay, silica,talcum powder, rice husk ash, and ash.
 9. A solid, biodegradableconcentrate carrier system for use in thermoplastic or thermosettingresin formulations, the concentrate comprising: an acrylate copolymercomprising less than 20 wt. % of the concentrate carrier system; one ormore aliphatic linear polyester elements selected from polycaprolactone,polyhydroxyalkonates, polyglycolide, polylactide, poly(butylenesuccinate), and any of the foregoing optionally having one or morefunctional groups pendant thereto, said aliphatic linear polyesterelement(s) cumulatively comprising less than 55 wt. % of the concentratecarrier system; an additive package comprising a remainder of theconcentrate, said additive package including at least one selected from:a plasticizer, a colorant, a property enhancer, and a non-propertyfillers; and wherein the concentrate carrier system retains a solid format ambient temperatures and the additive package remains viable in lowmelting resin systems and engineered resin systems at processingtemperatures ranging from 90° C. or less up to at least 200° C.
 10. Theconcentrate carrier system of claim 9 wherein the aliphatic linearpolyester element(s) is between 17.0 to 45.0 wt. % of the concentratecarrier system.
 11. The concentrate carrier system of claim 10 whereinthe aliphatic linear polyester elements are one selected from:polylactide, polybutylene succinate, and either or both of the foregoinghaving one or more functional groups pendant thereto.
 12. Theconcentrate carrier system of claim 11 wherein the acrylate copolymer isethyl-methyl acrylate provided at less than 5.0 wt. % of the concentratecarrier system.
 13. The concentrate carrier system of claim 9 whereinthe acrylate copolymer is ethyl-methyl acrylate provided at less than5.0 wt. % of the concentrate carrier system.
 14. The concentrate carriersystem of claim 9 wherein the aliphatic linear polyester elements arecumulatively less than 30 wt. % of the concentrate carrier system. 15.The concentrate carrier system of claim 9 wherein the aliphatic linearpolyester element is polyhydroxyalkonates optionally having one or morefunctional groups pendant thereto.
 16. The concentrate carrier system ofclaim 9 wherein the aliphatic linear polyester element is polyglycolideoptionally having one or more functional groups pendant thereto.
 17. Theconcentrate carrier system of claim 9 wherein the aliphatic linearpolyester element is polylactide optionally having one or morefunctional groups pendant thereto.
 18. The concentrate carrier system ofclaim 9 wherein the aliphatic linear polyester element is poly(butylenesuccinate) optionally having one or more functional groups pendantthereto.
 19. The concentrate carrier system of claim 9 wherein thealiphatic linear polyester element(s) all have a melting point of 160°C. or less.